Permanganate oxidation of unsaturated alcohols in alkaline media

Jáky, M.; Simon‐Trompler, Edit

doi:10.1002/kin.10080

Cited by 5 publications

(3 citation statements)

References 47 publications

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“…Although the acceleration can usually be detected from the beginning of the reactions, in the case of acid solutions, a phenomenon of delayed autocatalysis has been reported. − Whereas the autocatalysis found in acid media can be explained by the joint contributions of the Mn(II) ion formed as a reaction product (acting as a reducing agent for permanganate ion) and the colloidal Mn(IV) formed as a long-lived intermediate (acting as a heterogeneous catalyst for the reaction), that found in neutral media can be explained by the sole contribution of the colloidal Mn(IV) formed as the autocatalytic reaction product. This interpretation of the nature of the autocatalysts is consistent with the finding that the permanganate oxidations of organic substrates in alkaline media, where the inorganic product is Mn(VI) and lower oxidation states [from Mn(IV) to Mn(II)] are not expected to be involved in the mechanism as either intermediates or reaction products, present no observable autocatalysis. , Conversely, in the permanganate oxidation of oxalic acid in aqueous sulfuric media, autocatalysis has been reported to be caused by the lower oxidation states of manganese, with the long-lived intermediate colloidal Mn(IV) playing a crucial role in the mechanism of the autocatalytic reaction pathway …”

Section: Introductionsupporting

confidence: 80%

“…This interpretation of the nature of the autocatalysts is consistent with the finding that the permanganate oxidations of organic substrates in alkaline media, where the inorganic product is Mn(VI) and lower oxidation states [from Mn(IV) to Mn(II)] are not expected to be involved in the mechanism as either intermediates or reaction products, present no observable autocatalysis. 47,48 Conversely, in the permanganate oxidation of oxalic acid in aqueous sulfuric media, autocatalysis has been reported to be caused by the lower oxidation states of manganese, with the long-lived intermediate colloidal Mn(IV) playing a crucial role in the mechanism of the autocatalytic reaction pathway. 49 When the permanganate oxidations of organic compounds are performed in phosphate-buffered aqueous solutions, the reaction rate can be notably affected by the concentration of phosphate ions in different ways.…”

Section: ' Introductionmentioning

confidence: 99%

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Permanganate Oxidation of α-Amino Acids: Kinetic Correlations for the Nonautocatalytic and Autocatalytic Reaction Pathways

Perez‐Benito

2011

J. Phys. Chem. A

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The reactions of permanganate ion with seven -amino acids in aqueous KH 2 PO 4 -K 2 HPO 4 buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO 4 -) and 418 nm (formation of colloidal MnO 2 ). All the reactions studied were autocatalyzed by colloidal MnO 2 , the contribution of the autocatalytic reaction pathwayThe rate constants corresponding to the non-autocatalytic and autocatalytic pathways have been obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways have been determined and analyzed in order to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the non-autocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the -amino acid.Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (non-autocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.3

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Section: Introductionsupporting

confidence: 80%

Section: ' Introductionmentioning

confidence: 99%

Permanganate Oxidation of α-Amino Acids: Kinetic Correlations for the Nonautocatalytic and Autocatalytic Reaction Pathways

Perez‐Benito

2011

J. Phys. Chem. A

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“…On the other hand, the produced reactive intermediates in the reaction of permanganate with humic acid can be further reduced to lower valence of manganese species either by estrone or by humic acid, or may undergo disproportionation or oxidation by MnO 2 4 to other oxidation states of manganese ( Jaky & Simon-Trompler 2002;Wiberg et al 2006;Ahmed et al 2007). However, it is possible that the selective reaction between estrone and those reactive species may cause the decrease of estrone concencetration correspondingly.…”

Section: Effect Of Humic Acid On Estrone Degradationmentioning

confidence: 97%

Effect of humic acid on the oxidation of phenolic endocrine disrupting chemicals by permanganate

Shao

Yang

et al. 2010

Journal of Water Supply: Research and Technology-Aqua

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The effect of dissolved humic acid on the oxidation of phenolic endocrine disrupting chemicals (EDCs) by potassium permanganate was studied. It was found that the degradation of phenolic EDCs is promoted to various extents by the addition of humic acid. Results show that the removal rate of estrone by permanganate within 3 min of reaction time is increased from approximately 10% in control experiments to 68% when 0.08 mg l 21 of humic acid is present in the reaction system. The oxidation experiment of nine types of phenolic EDC by permanganate confirms that the promotion induced by the addition of humic acid varies in the cases of different EDCS. Results also indicate that the promotion induced by the presence of humic acid takes effect under acidic and neutral pH conditions, while the effect of pH plays a dominant role for the degradation of phenolic EDCs under alkaline conditions. Additionally, it was found that the oxidation of estrone by permanganate is promoted through the addition of humic acid to natural waters.

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Oligonucleotide Analogues with Integrated Bases and Backbone. Part 16

Zhang

Bernet

Vasella

2007

Helvetica Chimica Acta

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The self‐complementary, ethylene‐linked U*[ca]A(*) dinucleotide analogues 8, 10, 12, 14, 16, and 18, and the sequence‐isomeric A*[ca]U(*) analogues 20, 22, 24, 26, 28, and 30 were obtained by Pd/C‐catalyzed hydrogenation of the corresponding, known ethynylene‐linked dimers. The association of the ethylene‐linked dimers was investigated by NMR and CD spectroscopy. The U*[ca]A(*) dimers form linear duplexes and higher associates (K between 29 and 114M−1). The A*[ca]U(*) dimers, while associating more strongly (K between 88 and 345M−1), lead mostly to linear duplexes and higher associates; they form only minor amounts of cyclic duplexes. The enthalpy–entropy compensation characterizing the association of the U*[cx]A(*) and A*[cx]U(*) dimers (x=y, e, and a) is discussed.

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Permanganate oxidation of unsaturated alcohols in alkaline media

Cited by 5 publications

References 47 publications

Permanganate Oxidation of α-Amino Acids: Kinetic Correlations for the Nonautocatalytic and Autocatalytic Reaction Pathways

Permanganate Oxidation of α-Amino Acids: Kinetic Correlations for the Nonautocatalytic and Autocatalytic Reaction Pathways

Effect of humic acid on the oxidation of phenolic endocrine disrupting chemicals by permanganate

Oligonucleotide Analogues with Integrated Bases and Backbone. Part 16

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